Triarylamine crosslinking molecules with halogenated styrene side chains, methods of making and using the same

Abstract

This invention discloses a triarylamine crosslinked molecule with a halostyrene side chain, its preparation method, and its applications, belonging to the field of optoelectronic materials technology. This triarylamine crosslinked molecule with a halostyrene side chain exhibits good structural symmetry and good orbital separation characteristics, effectively suppressing nonradiative recombination of electrons and holes during carrier transport, which is beneficial to improving the carrier separation and transport efficiency of the device. When applied to the fabrication of perovskite solar cells, it improves the photoelectric performance of the device. Single-electron and single-hole device tests show that after adding this crosslinked molecule, the trap filling threshold voltage is significantly reduced, the trap density decreases, and the electron mobility and hole mobility increase. This crosslinked molecule can effectively passivate perovskite defects and improve carrier transport capability, making it suitable for high-efficiency and stable perovskite solar cells.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic materials, and in particular to a triarylamine crosslinked molecule with a halostyrene side chain, its preparation method, and its application in perovskite solar cells. Background Technology

[0002] Triarylamine compounds are widely used in organic optoelectronic devices, such as organic light-emitting diodes (OLEDs) and perovskite solar cells (PSCs), due to their excellent hole transport capabilities and good film-forming properties.

[0003] Organic-inorganic hybrid perovskite solar cells are a key area for next-generation photovoltaic technology due to their ease of manufacture, cost-effectiveness, and excellent photoelectric properties. However, perovskite solar cells are susceptible to environmental influences, leading to performance degradation. Among the many influencing factors, perovskite solar cells, due to their unique chemical properties, are prone to degradation in humid environments. Currently, there are two main methods to mitigate the degradation caused by moisture. One method is to introduce a passivation layer between the functional layers to prevent moisture or oxygen from eroding the perovskite. The other method is to introduce additives into the perovskite precursor solution to improve the crystallinity of the perovskite. Compared to small-molecule additives, polymer additives offer significantly improved stability and moisture resistance. However, most polymers have poor conductivity and lack carrier transport capabilities, which can affect carrier transport during cell operation, thus impacting device performance.

[0004] Based on the above problems, a triarylamine crosslinked molecule with a halogenated styrene side chain and its preparation method are proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a triarylamine crosslinking molecule with a halogenated styrene side chain, its preparation method, and its application. This invention aims to solve the problems of low crystal quality and poor interface stability of the perovskite layer in existing perovskite solar cells. By adding the crosslinking molecule to the perovskite precursor solution and crosslinking it under ultraviolet light irradiation, the morphology of the perovskite film and the device stability are significantly improved.

[0006] To achieve the above objectives, the present invention provides a triarylamine crosslinked molecule with a halostyrene side chain, wherein the triarylamine crosslinked molecule with the halostyrene side chain is either molecule one or molecule two, and the structural formula of molecule one is as follows: ; The structural formula of molecule II is: ; Where R is the number of carbon atoms, ranging from 0 to n; x is one of F, Cl, and Br.

[0007] Preferably, the structural formula of the triarylamine crosslinked molecule with the halogenated styrene side chain is one of the following a~l: .

[0008] This invention also provides a method for preparing the above-mentioned triarylamine crosslinked molecules with halostyrene side chains. The synthetic route of molecule one is as follows: ; The synthetic route for molecule II is as follows: .

[0009] Preferably, the specific preparation steps of molecule one are as follows: S1. Preparation of intermediate 1: Halophenol, base and DMF are added to the reaction flask, nitrogen is purged three times, and the reaction is carried out at room temperature for 1 hour. Then halostyrene is added and the reaction is carried out at 40~80℃ for 2 hours to obtain intermediate 1. S2. Preparation of molecule one: Intermediate 1, diamine monomer, tri-tert-butylphosphine, sodium tert-butoxide, target catalyst and toluene are added to a reaction flask, purged with nitrogen three times, and incubated overnight at 100°C to obtain molecule one.

[0010] Preferably, in S1, the molar ratio of halogenated phenol to base is 0.9~1.2:2, and the base is potassium carbonate; the molar ratio of halogenated phenol to halogenated styrene is 1~1.2:1; the halogenated phenol is 4-iodophenol, and the halogenated styrene is 1,2,3,4,5-pentafluoro-6-vinylbenzene; In S2, the molar ratio of intermediate 1 to diamine monomer is 2-2.5:1, the molar ratio of tri-tert-butylphosphine to intermediate 1 is 0.01-0.05:1, the molar ratio of sodium tert-butoxide to intermediate 1 is 1-2:1, and the molar ratio of target catalyst to intermediate 1 is 0.01-0.03:1; the diamine monomer is N,N-diphenylbiphenyldiamine, and the target catalyst is tris(dibenzylacetone)dipalladium.

[0011] Preferably, the specific preparation steps of molecule two are as follows: S1. Preparation of intermediate 2: Aromatic amine, polyhalogenated aromatic hydrocarbon, base and anhydrous DMF are added to the reaction flask, nitrogen is purged three times, and the reaction is carried out at 0°C for 3 hours. Then the temperature is raised to 100°C and left overnight to obtain intermediate 2. S2. Preparation of intermediate 3: Intermediate 2 and dichloromethane were added to a reaction flask, and after purging with nitrogen three times, boron tribromide was added at -30°C and the reaction was carried out overnight to obtain intermediate 3. S3. Preparation of molecule II: Add intermediate 3, base and DMF to the reaction flask, purge with nitrogen three times, stir at room temperature for 1-2 hours, add halostyrene, and react overnight to obtain molecule II.

[0012] Preferably, in S1, the molar ratio of aromatic amine to polyhalogenated aromatic hydrocarbon is 2~3:1, and the molar ratio of base to polyhalogenated aromatic hydrocarbon is 2~3:1; the base is sodium hydride; the aromatic amine is 4-methoxy-N-phenylaniline, and the polyhalogenated aromatic hydrocarbon is perfluorobiphenyl; In S2, the molar ratio of intermediate 2 to boron tribromide is 1:3~4; In S3, the molar ratio of intermediate 3 to base is 1:3~4, and the base is cesium carbonate; the molar ratio of intermediate 3 to halostyrene is 1:2~3; and the halostyrene is 1,2,3,4,5-pentafluoro-6-vinylbenzene.

[0013] The present invention also provides an application of triarylamine crosslinking molecules with halostyrene side chains, which are used in the fabrication of perovskite solar cells.

[0014] Preferably, triarylamine crosslinking molecules of halogenated styrene side chains are doped into the light-absorbing layer of the perovskite solar cell. The specific method is as follows: triarylamine crosslinking molecules of halogenated styrene side chains are added to the perovskite precursor solution, a perovskite wet film is formed by spin coating, the crosslinking molecules are crosslinked by ultraviolet light irradiation, and then the perovskite light-absorbing layer is formed by annealing.

[0015] Preferably, the method for fabricating a perovskite solar cell includes the following steps: Step 1: Clean the transparent conductive substrate and deposit an electron transport layer; Step 2: Prepare a perovskite precursor solution containing triarylamine crosslinked molecules with halostyrene side chains; Step 3: Coat the precursor solution onto the electron transport layer, anneal it after irradiation with ultraviolet light to form a perovskite light absorption layer. Step 4: Prepare a hole transport layer and a metal electrode on the perovskite layer.

[0016] Therefore, this invention relates to a triarylamine crosslinked molecule with a halostyrene side chain, its preparation method, and its application. The two prepared triarylamine crosslinked molecules with halostyrene side chains both exhibit good structural symmetry and demonstrate good orbital separation characteristics, effectively suppressing nonradiative recombination of electrons and holes during carrier transport. This is beneficial for improving carrier separation and transport efficiency in devices, thereby improving the optoelectronic performance of the devices. The fluorine atoms introduced into the molecules not only increase the hydrophobicity of the material, thus enhancing the perovskite's resistance to moisture, but also react with Pb in the perovskite. 2+ It forms an effective coordination effect, passivates perovskite surface and grain boundary defects, and inhibits the generation of non-radiative recombination centers, thereby stabilizing the perovskite active layer and improving device stability.

[0017] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0018] Figure 1 This is a comparison chart of the photoelectric conversion efficiency of Application Example 1 and Application Comparative Example 1 of the present invention; Figure 2 The JV curves of the single electronic devices obtained in Application Examples 3 and 4 and Comparative Example 2 of this invention are shown. Figure 3 The JV curves of the single-hole devices obtained in Application Examples 5 and 6 and Comparative Example 3 of the present invention are shown. Detailed Implementation

[0019] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0021] Example 1 In this embodiment, molecule one is prepared, and its synthetic route is as follows: .

[0022] The specific preparation steps are as follows: S1. Preparation of Intermediate 1: 1.50 g (6.82 mmol) of 4-iodophenol, 1.88 g (13.64 mmol) of potassium carbonate, and 36 mL (545.43 mmol) of N,N-dimethylformamide (DMF) were added to a reaction flask. The mixture was purged with nitrogen three times to remove oxygen from the system. After reacting at room temperature for 1 h, 1.46 g (7.50 mmol) of 1,2,3,4,5-pentafluoro-6-vinylbenzene was added to the reaction flask and reacted at 60 °C for 2 h to obtain 1.60 g (11.38 mmol) of Intermediate 1, with a yield of 60%.

[0023] The structure of the obtained product was characterized. 1 H NMR (400 MHz, Chloroform-d) 7.62 (d, J =9.0 Hz, 2H), 6.76 (d, J = 8.8 Hz, 2H), 6.72-6.63 (m, 1H), 6.12 (d, J = 18.0Hz, 1H), 5.73 (d, J = 12.0 Hz, 1H). S2. Preparation of molecule one: 1.50 g (3.81 mmol) of intermediate 1, 0.63 g (1.71 mmol) of N,N-diphenylbiphenyldiamine (compound 9), 0.12 mg (570.91 µmol) of tri-tert-butylphosphine, 0.55 g (5.71 mmol) of sodium tert-butoxide, 0.18 mg (190.30 µmol) of tris(dibenzylideneacetone)dipalladium and 48 mL (456.73 mmol) of toluene were added to a reaction flask. The mixture was purged with nitrogen three times to remove oxygen from the system. The reaction was carried out overnight at 100 °C to obtain 1.50 g (1.67 mmol) of molecule one, with a yield of 44%.

[0024] The structure of the obtained product was characterized. 1 H NMR (400 MHz, Chloroform-d) δ 7.40 (d, J =5.7 Hz, 4H), 7.05 (d, J = 21.7 Hz, 16H), 6.88 (d, J = 8.2 Hz, 4H), 6.68 (dd,J = 18.0, 11.9 Hz, 2H), 6.10 (d, J = 18.0 Hz, 2H), 5.71 (d, J = 11.9 Hz, 2H), 2.32 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 152.81, 146.84, 146.18, 144.19,142.68, 142.56, 140.70, 140.57, 134.20, 132.81, 132.71, 132.61, 129.99,127.18, 125.60, 124.59, 124.58, 123.34, 123.28, 123.22, 122.97, 121.94,116.60, 113.11, 113.00, 112.89, 20.83. HRMS (APCI + m / z: calculated value for C 54 H 36 F8N2O2[M+H] + 896.265, found value [M+H] + 896.172. Example 2 In this embodiment, molecule II is prepared, and its synthetic route is as follows: .

[0025] The specific preparation steps are as follows: S1. Preparation of Intermediate 2: 6.56 g (32.92 mmol) of 4-methoxy-N-phenylaniline, 5.00 g (14.96 mmol) of perfluorobiphenyl, and 1.50 g (37.41 mmol) of sodium hydride (60% wt) were added to a reaction flask. The mixture was purged with nitrogen three times to remove oxygen. 70 mL (897.89 mmol) of anhydrous DMF was added at 0 °C and the mixture was reacted for 3 h, then the temperature was raised to 100 °C and reacted overnight. 4.80 g of Intermediate 2 was obtained, with a yield of 46%.

[0026] The structure of the obtained product was characterized. 1 H NMR (800 MHz, Chloroform-d) δ 7.27 (d, J =8.4 Hz, 4H), 7.14 (d, J = 8.9 Hz, 4H), 7.02 (t, J = 7.4 Hz, 2H), 6.91 (dd, J= 18.5, 8.4 Hz, 8H), 3.82 (s, 6H). HRMS (APCI + m / z: calculated value for C 38 H 24 F8N2O2[M+H] + 692.171, found value [M+H] + 692.057. S2. Preparation of Intermediate 3: 4.50 g (6.50 mmol) of Intermediate 2 and 30 mL (480.79 mmol) of dichloromethane were added to a reaction flask, and the mixture was purged with nitrogen three times to remove oxygen from the system. 5.86 g of boron tribromide (23.39 mmol) was added at -30 °C and the reaction was carried out overnight to give 2.50 g of Intermediate 3, with a yield of 58%.

[0027] The structure of the obtained product was characterized. 1 H NMR (500 MHz, DMSO-d6) δ 9.55 (s, 2H), 7.29– 7.26 (m, 4H), 7.05 (d, J = 8.7 Hz, 4H), 7.00 (t, J = 7.3 Hz, 2H), 6.91 (d,J = 8.0 Hz, 4H), 6.79 (d, J = 8.8 Hz, 4H). HRMS (APCI + m / z: calculated value for C 36 H 20 F8N2O2[M+H] +664.140, found value [M+H] + 664.048. S3. Preparation of Molecular II: 1.20 g (1.81 mmol) of intermediate 3, 1.77 g (5.42 mmol) of cesium carbonate, and 15 mL (180.57 mmol) of DMF were added to a reaction flask. The mixture was purged with nitrogen three times to remove oxygen. After stirring at room temperature for 1 h, 0.8 g (4.51 mmol) of 1,2,3,4,5-pentafluoro-6-vinylbenzene was added and the mixture was reacted overnight to give 1.30 g of Molecular II, with a yield of 71%.

[0028] The structure of the obtained product was characterized. 1 H NMR (800 MHz, Chloroform-d) δ 7.32-7.29 (m,4H), 7.09 (d, J = 8.9 Hz, 6H), 6.99 (dd, J = 33.9, 8.4 Hz, 8H), 6.68 (dd, J =18.0, 11.9 Hz, 2H), 6.11 (d, J = 18.0 Hz, 2H), 5.72 (d, J = 11.9 Hz, 2H). 13CNMR (126 MHz, CDCl3) δ 153.92, 146.18, 145.87, 145.34, 144.19, 143.91,143.40, 143.30, 142.63, 142.51, 141.34, 140.63, 140.51, 129.50, 124.53,123.54, 123.50, 123.44, 123.38, 121.88, 120.89, 116.83, 113.37, 113.26,113.15, 103.29. HRMS (APCI + ) m / z: calculated value for C 52 H 24 F 16 N₂O₂[M+H] + 1012.158, found value [M+H] + 1012.037. The triarylamine crosslinked molecules with halogenated styrene side chains prepared in this invention are applied to the fabrication of perovskite solar cells.

[0029] Application Example 1: The structure of the perovskite solar cell is FTO / c-TiO2 / m-TiO2 / perovskite / Spiro-OMeTAD / Au.

[0030] The specific preparation steps are as follows: Step 1: The FTO glass substrate is ultrasonically cleaned in deionized water, ethanol, isopropanol and ethanol for 15 minutes in sequence, and then treated with oxygen plasma for 10 minutes to enhance the surface hydrophilicity and remove residual organic contaminants.

[0031] Step 2: Subsequently, a dense TiO2 (c-TiO2) layer was deposited by spray pyrolysis at 470°C; the c-TiO2 precursor solution was prepared by dissolving 600 μL of diisopropoxybisacetylacetonate titanium (75 wt.% isopropanol solution) and 400 μL of acetylacetone in 9 mL of anhydrous isopropanol.

[0032] Step 3: Dissolve TiO2 slurry in ethanol at a weight ratio of 1:7, spin coat it onto c-TiO2 at 4000 rpm for 20 seconds, sinter at 500℃ for 30 minutes, and then transfer it into a glove box to obtain a mesoporous TiO2 (m-TiO2) layer.

[0033] Step 4: The perovskite precursor solution containing the triarylamine crosslinked molecules with halostyrene side chains prepared in Example 1 is dropped onto the electron transport layer and coated using a two-step spin-coating method. First, spin-coat at 1000 rpm for 10 seconds; then spin-coat at 6000 rpm for 20 seconds. Five seconds before the end, 100 μL of chlorobenzene is dropped as an antisolvent. Then, irradiate with ultraviolet light for 5 seconds and anneal at 120°C for 20 minutes.

[0034] Step 5: Dissolve Spiro-OMeTAD, Li-TFSI solution (acetonitrile 520 mg / mL), and t-BP in 1 mL of chlorobenzene to prepare a hole transport material solution. Spin-coat this solution onto a perovskite film at 4000 rpm for 20 seconds, place it in a desiccator, and oxidize it overnight at room temperature. Finally, evaporate under vacuum (low pressure < 1 × 10⁻⁶). -4 A 100 nm gold electrode was deposited using Pa) to obtain a perovskite solar cell.

[0035] Application Example 2 This application example is the same as the steps in application example 1, except that step 4 is modified as follows: the triarylamine crosslinked molecules of the halostyrene side chain prepared in example 2 are added to the perovskite precursor solution.

[0036] Application Comparative Example 1 The comparative example of this application follows the same steps as Application Example 1, except that step 4 is modified to: triarylamine crosslinked molecules without adding halostyrene side chains.

[0037] The photoelectric conversion efficiency comparison data of the solar cells prepared in Application Example 1 and Application Comparative Example 1 are as follows: Figure 1 As shown.

[0038] Single-carrier devices were fabricated using the triarylamine crosslinked molecules obtained in Examples 1 and 2, respectively.

[0039] Application Example 3 In this embodiment, a single-electron device was prepared using the triarylamine crosslinked molecule with halogenated styrene side chains obtained in Example 1. The device structure is: ITO / SnO2 / perovskite / PCBM / Au.

[0040] The specific preparation steps are as follows: (1) Substrate treatment: Dissolve the conductive glass cleaner in deionized water at a ratio of 1:50 (v:v) to prepare the cleaning solution. Use the cleaning solution, deionized water, ethanol, isopropanol, ethanol and ethanol in sequence to ultrasonically clean the ITO conductive glass for 15 min. After cleaning, blow it dry with nitrogen gas for later use.

[0041] (2) SnO2 preparation: SnO2 colloidal dispersion was dissolved in water at a ratio of 1:5 (v:v) and sonicated for 30 min. The resulting ETM solution was spin-coated onto an ITO substrate at a speed of 3000 rpm (acceleration of 1500 rpm). After spin-coating, the ITO was transferred to a hot plate and annealed at 150℃ for 30 min.

[0042] (3) A solution of perovskite precursor containing triarylamine crosslinked molecules with halostyrene side chains prepared in Example 1 was dropped onto the electron transport layer and coated using a two-step spin-coating method. First, spin-coating was performed at 1000 rpm for 10 seconds; then at 6000 rpm for 20 seconds. Five seconds before the end, 100 μL of chlorobenzene was dropped as an antisolvent. Then, the mixture was irradiated with ultraviolet light for 5 seconds and annealed at 120°C for 20 minutes.

[0043] (4) Preparation of PCBM: PCBM was dissolved in chlorobenzene. The resulting solution was spin-coated onto perovskite at a speed of 3000 rpm (acceleration of 1500 rpm). After spin-coating, the solution was annealed at 100°C for 10 min.

[0044] (5) Finally, vacuum evaporation (low pressure <1×10) is performed. -4 A 100 nm gold electrode was deposited using Pa) to obtain a perovskite solar cell.

[0045] Application Example 4 In this embodiment, a single-electron device was prepared using the triarylamine crosslinked molecule with halogenated styrene side chains obtained in Example 2. The device structure and preparation steps are the same as in Application Example 3.

[0046] Application Comparative Example 2 The comparative example of this application is prepared using the same method as application example 3, the only difference being that no triarylamine crosslinking molecule with a halogenated styrene side chain is added.

[0047] Application Example 5 In this embodiment, a single-hole device was prepared using the triarylamine crosslinked molecule with halogenated styrene side chains obtained in Example 1. The device structure is: ITO / PEDOT:PSS / perovskite / Au.

[0048] The specific preparation steps are as follows: (1) Substrate treatment: Dissolve the conductive glass cleaner in deionized water at a ratio of 1:50 (v:v) to prepare the cleaning solution. Use the cleaning solution, deionized water, ethanol, isopropanol, ethanol and ethanol in sequence to ultrasonically clean the ITO conductive glass for 15 min. After cleaning, blow it dry with nitrogen gas for later use.

[0049] (2) Preparation of PEDOT:PSS: The PEDOT:PSS solution was spin-coated onto the ITO substrate at a speed of 3000 rpm (acceleration of 1500 rpm). After spin-coating, the ITO was transferred to a hot plate and annealed at 150°C for 30 min.

[0050] (3) A solution of perovskite precursor containing triarylamine crosslinked molecules with halostyrene side chains prepared in Example 1 was dropped onto the electron transport layer and coated using a two-step spin-coating method. First, spin-coating was performed at 1000 rpm for 10 seconds; then at 6000 rpm for 20 seconds. Five seconds before the end, 100 μL of chlorobenzene was dropped as an antisolvent. Then, the mixture was irradiated with ultraviolet light for 5 seconds and annealed at 120°C for 20 minutes.

[0051] (4) Finally, vacuum evaporation (low pressure <1×10) -4 A 100 nm gold electrode was deposited using Pa) to obtain a perovskite solar cell.

[0052] Application Example 6 In this embodiment, a single-hole device was prepared using the triarylamine crosslinked molecule with halogenated styrene side chain obtained in Example 2. The device structure and preparation steps are the same as in Application Example 5.

[0053] Application Comparative Example 3 The comparative example of this application is prepared using the same method as application example 5, the only difference being that no triarylamine crosslinking molecule with a halogenated styrene side chain is added.

[0054] The current-voltage (JV) curves of the single-electron device and the single-hole device were measured in the dark, as follows: Figure 2 , Figure 3 As shown in Table 1, the trap filling limit voltage (VTFL), trap density, and electron mobility were calculated using a space charge-limited current model.

[0055] Table 1: Comparison of Electrical Parameters

[0056] As shown in Table 1, perovskite films with added crosslinking molecules exhibit lower trap density and higher carrier mobility in both single-electron and single-hole devices. Among them, triarylamine crosslinking molecules with halostyrene side chains have better defect passivation and charge transport promotion capabilities, especially for hole mobility.

[0057] This indicates that the triarylamine crosslinking molecules with halogenated styrene side chains provided by the present invention can effectively reduce the trap state density in perovskite films and simultaneously improve the transport capabilities of electrons and holes, which is beneficial to improving the photoelectric conversion efficiency and fill factor of perovskite solar cells.

[0058] Therefore, this invention discloses a triarylamine crosslinking molecule with halostyrene side chains, its preparation method, and its application. The prepared triarylamine crosslinking molecule with halostyrene side chains can be rapidly crosslinked under ultraviolet light to form a stable three-dimensional network structure, effectively fixing perovskite crystals, inhibiting ion migration, and improving device stability. The crosslinking molecule is directly added to the perovskite precursor solution, simplifying the process, eliminating the need for additional film-forming steps, and exhibiting good compatibility with existing perovskite solar cell fabrication processes. The solvent resistance and charge extraction capability of the crosslinked film are significantly improved, and the photoelectric conversion efficiency and long-term stability of the device are also enhanced.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A triarylamine crosslinked molecule with a halostyrene side chain, characterized in that: The triaryl amine crosslinked molecule with the side chain of halostyrene is either molecule one or molecule two. The structural formula of molecule one is: ； The structural formula of molecule II is: ； Where R is the number of carbon atoms, ranging from 0 to n; x is one of F, Cl, and Br.

2. The triarylamine crosslinked molecule with a halostyrene side chain according to claim 1, characterized in that, The structural formula of the triarylamine crosslinked molecule with halostyrene side chain is one of the following a~l: 。 3. A method for preparing a triarylamine crosslinked molecule with a halostyrene side chain as described in any one of claims 1-2, characterized in that, The synthetic route for molecule one is as follows: ； The synthetic route for molecule II is as follows: 。 4. The preparation method according to claim 3, characterized in that, The specific preparation steps for molecule one are as follows: S1. Preparation of intermediate 1: Halophenol, base and DMF are added to the reaction flask, nitrogen is purged three times, and the reaction is carried out at room temperature for 1 hour. Then halostyrene is added and the reaction is carried out at 40~80℃ for 2 hours to obtain intermediate 1. S2. Preparation of molecule one: Intermediate 1, diamine monomer, tri-tert-butylphosphine, sodium tert-butoxide, target catalyst and toluene are added to a reaction flask, purged with nitrogen three times, and incubated overnight at 100°C to obtain molecule one.

5. The preparation method according to claim 4, characterized in that: In S1, the molar ratio of halophenol to base is 0.9~1.2:2, and the base is potassium carbonate; the molar ratio of halophenol to halostyrene is 1~1.2:1; the halophenol is 4-iodophenol, and the halostyrene is 1,2,3,4,5-pentafluoro-6-vinylbenzene. In S2, the molar ratio of intermediate 1 to diamine monomer is 2-2.5:1, the molar ratio of tri-tert-butylphosphine to intermediate 1 is 0.01-0.05:1, the molar ratio of sodium tert-butoxide to intermediate 1 is 1-2:1, and the molar ratio of target catalyst to intermediate 1 is 0.01-0.03:1; the diamine monomer is N,N-diphenylbiphenyldiamine, and the target catalyst is tris(dibenzylacetone)dipalladium.

6. The preparation method according to claim 3, characterized in that, The specific preparation steps for molecule II are as follows: S1. Preparation of intermediate 2: Aromatic amine, polyhalogenated aromatic hydrocarbon, base and anhydrous DMF are added to a reaction flask, nitrogen is purged three times, the reaction is carried out at 0℃ for 3 hours, and then the temperature is raised to 100℃ overnight to obtain intermediate 2. S2. Preparation of intermediate 3: Intermediate 2 and dichloromethane were added to a reaction flask, and after purging with nitrogen three times, boron tribromide was added at -30°C and the reaction was carried out overnight to obtain intermediate 3. S3. Preparation of molecule II: Add intermediate 3, base and DMF to the reaction flask, purge with nitrogen three times, stir at room temperature for 1-2 hours, add halostyrene, and react overnight to obtain molecule II.

7. The preparation method according to claim 6, characterized in that: In S1, the molar ratio of aromatic amine to polyhalogenated aromatic hydrocarbon is 2~3:1, and the molar ratio of base to polyhalogenated aromatic hydrocarbon is 2~3:1; the base is sodium hydride; the aromatic amine is 4-methoxy-N-phenylaniline, and the polyhalogenated aromatic hydrocarbon is perfluorobiphenyl; In S2, the molar ratio of intermediate 2 to boron tribromide is 1:3~4; In S3, the molar ratio of intermediate 3 to base is 1:3~4, and the base is cesium carbonate; the molar ratio of intermediate 3 to halostyrene is 1:2~3; and the halostyrene is 1,2,3,4,5-pentafluoro-6-vinylbenzene.

8. The application of a triarylamine crosslinked molecule with a halostyrene side chain as described in any one of claims 1-2, characterized in that: Triarylamine crosslinked molecules with halogenated styrene side chains are applied to the fabrication of perovskite solar cells.

9. The application according to claim 8, characterized in that: The triaryl amine crosslinking molecules of halogenated styrene side chains are doped into the light absorption layer of perovskite solar cells. The specific method is as follows: the triaryl amine crosslinking molecules of halogenated styrene side chains are added to the perovskite precursor solution, a perovskite wet film is formed by spin coating, the crosslinking molecules are crosslinked by ultraviolet light irradiation, and then the perovskite light absorption layer is formed by annealing.

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